Manufacture of intermediate oxidation products



1931. J. H.-JAMES 1,836,325

MANUFACTURE OF INTERMEDIATE OXIDATION- PROD/UCTS r/fj Original FiledJan. 18, 1926 5 Sheets-Sheet l "L; at v J. H. JAMES 36,325

MANUFACTURE OF INTERMEDIATE OXIDATION PRODUCTS Dec. '15, 1931.

Original Filed Jan. 18, 1926 5 Shee s-Sheet 2 INVENTOR Dec. 15, 1931.

H.JAMES MANUFACTURE OF INTERMEDIATE OXIDATION PRODUCTS Original FiledJan. 18, 1926 5 Sheets-Shee 5 ullllllll A J. H. JAMES 1,836,325

MANUFACTURE OF INTERMEDIATE OXIDATION PRODUCTS Dec. 15, 1931.

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Original Filed Jan. 18, 1926 59. EB: m ms mwm mw D86. 15, 1931. J H,JAMES 1,836,325

MANUFACTURE OF INTERMEDIATE OXIDATION PRODUCTS Original FiledJan. 18,1926 5 Sheets-Sheet 5 E6 INVENTOR av-4 m n- M Patented Dec. 15, 1931UNITED STATES PATENT OFFICE JOSEPH H. JAMES, 01" PITTSBURGH,PENNSYLVANIA, .ASSIGNOR TO BYBNES, TRUSTEE, F SEWICKLEY, PENNSYLVANIACLARENCE P.

MANUFACTURE OF INTERMEDIATE OXIDATION PRODUCTS Application filed January18, 1926, Serial No. 81,963. Renewed Jnne27, 1927.'

In the drawings:

Figure 1 is a top plan view of a treating apparatus embodying theinvention;

Figure 2 is a vertical section on the 5, II-II of Figure 1;

Figure 3 is a side elevation, partly broken away, of another apparatusembodying the invention; 1

Figured is an end elevation of the apparatus shown in Figure 3;

Figure 5 is a vertical section on the line V-V of Figure 3;

Figure 6 is a horizontal section on the line VIVI of Figure 3;

Figure 7 is a vertical section on the line VIIVII of Figure 3;

Figure 8 is a diagrammatic plan view showing another system for carryingout my invention; and I Figure 9 is a side elevation, partly brokenaway, on a larger scale, showing the reaction" chamber and connectionsof the system of Figure 8. Y

My invention relates to the manufacture of line " intermediate oxidationproducts from or-- g'anic'bodies such forexample as hydrocarbons orhydrocarbons derivatives. It is especially advantageous in producingintermediate oxidation products from hydrocarbons or hydrocarbon,derivatives ofthe lower mo- 1 lecular weights such'asthose which aregaseous at normal temperatures and pressures, or

those hydrocarbon v liquids which are more volatile.

In a number of copending applications, for example, Serial No. 272,567,'filed January 22, 1919,;Serial No. 281,124, filedMarch 7 1919, SerialNo. 335,939., filed November 5, 1919, SerialNo. 435,355, filed January6, 1921, and Serial No. 520,283, filed December 6, 1921; I havedisclosed processes for making intermediate oxidation products frommineral hydrocarbons such as petroleum or fractions thereof, theproducts from the low temperature distillation of coals, and from shaleoil, whether or not said products-havebeen cracked prior to oxidation.In said processes the hydrocarbon, in vapor or gaseous phase, was mixedwlth oxygen or an oxygen containing gas such as air, and the mixturethe. reaction zone and removed t passed through a reaction zone at atemperature between 160 C. and 500 C. with; or without a catalyst. Thecondensed roducts of such processes were in the range fi'om aliphaticalcohols to aldehyde fatty acids including aldehydes, aldehyde alcohols,esters, ketones, etc.

Such processes, while generally a plicable, are specially desirable forliquid ydrocarbons having a boiling range from that of kerosene onthrough the mineral oil fractions of heavier molecular weights; but forfractions lighter than the lower kerosene limit, including gaseoushydrocarbons, the diluting effect of the nitrogen of the air makes itdifiicult to procure and recover the products. Furthermore, in thelighter hydrocarbons below the kerosene range, the explosive range ofsuch hydrocarbons when mixed withair becomes wider, thus increasing thehazard of working with the more volatile or gaseous hydrocarbons.

The present invention is designed to overcome or reduce thesedifliculties, and the main stream containing 'free oxygen, as forexample, by mixing the finely divided hydrocarbon with air. Theoperation is preferably carried out in an atmosphere free orsubstantially free of air or'free oxygen and at a reactive temperaturewhich will cause oxygen to pass from the oxygen-containing material intothe. hydrocarbon or hydrocarbon derivative. The material which is thuspartially or wholly deoxidized is withdrawn from the reaction zone andpreferably regenerated by reoxidizing it and then re-used in theprocess. The oxidant material containing the chemically-combined oxygenmay be supplied to erefrom either continuousl or intermittently, and ispreferably in finely divided form. It may thusbe supplied in the form ofa continuously or intermittentlyflowing stream or shower of finelydivided solid material which may be collected and trapped out; or it maybe supplied either continuously or intermittently by means of a movingcarrier such as a disk provided with an oxidant screen or screens whichmay be rotated or moved either continuously or intermittently, andthrough a portion of which the hydrocarbon stream is passed at atemperature within the reaction range. In either case, the materialwhich has been deoxidized either partially or wholly within the reactionzone, is preferably reoxidized, as for examplefby subjecting it at aproper temperature to the action of air and may then be re-used in theprocess.

When the powdered or finely divided oxidant material is used in showerform, it may be trapped out and reoxidized and again fed through thereaction zone; and in the case of the moving oxidant screen the portionsother than the portions through which the finely divided hydrocarbon ispassing may be subjected to heated air or kept heated in the presence ofair to cause the reoxidation before such portions again pass within thereaction zone.

In the preferred form, the operation is cyclic. In one passage of thefinely divided hydrocarbon through the oxidant, only a portion of thehydrocarbon will be partly oxidized. The vapor stream will then passthrough a condensation scrubbing and washing system to extract thepartial oxidation products. The remainder of the exit stream will thenagain pass through a reaction zone and the oxidizing operation berepeated, using either the same apparatus or another apparatus ofsimilar type. Fresh hydrocarbon is preferably supplied to the exitstream after extraction of the intermediate oxidation products and Iusually prefer to also tap out a portion of the remaining gaseous streamand supply fresh hydrocarbon suflicient to replace both the tapped outportion and the recovered portion which has been converted intointermediate oxidation products; before repeating the oxidation processeither in the same or a similar apparatus.

The material which I preferably employ as the oxidant preferablyconsists of metallic oxides and I have discovered that for this purposethe class of metallic oxides which I have disclosed as catalysts in thepending applications above referred to gives the best results. Suchoxides are those of the high melting-point, electronegative,low-atomicvolume metals, particularly those having an atomic weightabove 40. These metals appear on the Lothar-Meyer diagram of theperiodic series beginning on the descending side of the third peak andextending on the descending side of the fourth peak and the descendingside of further peaks later developed. This class includes the followingmetals: titanium, vanadium, chromium, manganese, zirconium, niobium,molybdenum, tantalum, tungsten and uranium. An excellent oxidant for mypresent purposes consists of the tri-oxide of molybdenum. I prefer toemploy the complex oxides of metals having a varyingvalence. The partsof the complex may consist of oxides of the same metal or of differentmetals. Such complexes may be regarded as salts, that is, compounds ofone or more basic acid oxides. The basic and acid parts of thesecomplexes may be formed from oxides of different metals, in which caseeach metal or group of metals used should possess varying valence. Thebasic oxides may be the lower oxides of the metals in the class named ormay be the oxides of iron, copper, nickel, lanthanum,

cobalt, thorium or eight or nine rare earth metals. In both acid orbasic portions there may, of course, be two or more of these combined. Imay use chromic-chromate, tungsten-tungstate, etc., for example.

It will be noted that in my new method the hydrocarbon or hydrocarbonderivative is in finely divided form, preferably in the vapor or gaseousphase, while the oxygen derived from a material containingchemically-combined oxygen and preferably in solid finely dividedcondition. The temperature will vary according to the hydrocarbon orhydrocarbon mixture being treated. Under the conditions named, thehydrocarbon can be partially oxidized to form intermediate products,such as alcohols, aldehydes-and acids. During the process, if a solidoxide is employed, the oxide will pass to a lower state of oxidation orto the metal itself.

In the preferred form, the operation is carried out in such a way andthe factors, such as rate of gas or vapor flow and feed of oxide, are socontrolled that only a part of the total hydrocarbon present isconverted during one passage. In such case, the residual hydrocarbon,together with any carbon dioxide present, is preferably returned to thesystem after adding fresh hydrocarbon to replace that converted andtaken up in the absorption system, as well as that which is tapped outif this tapping out is used. The tapping out of a portion of the exitgas beyond the absorbing system is specially desirable in the partialoxidation of hydrocarbons which are gaseous at ordinary temperatures andpressures.

In order to carry out this process, it is necessary to bring freshoxygen-containing material in contact with the stream of gas or vapor ofthe organic body being treated. In this process, the hydrocarbon must bein finely divided form, preferably either in the form of a gas or vapor,and hence, if normally a liquid or solid, it should be vaporized, thevapors or gases being brought in contact with the oxidant at a reactivetemperature which varies according to the hydrocarbon or hydrocarbonmixturebeing treated. For example, in the naaasas case of gases fromcracking stills containing olefin contents, the temperature may berelatively low (170 and upwards) on account of the unsaturated compoundspresent. In the ture should be much higher and nearer to but preferablybelow 600 C.

Throughout the specification and claims, where I use the word hdrocarbon, I intend to include hydrocar on derivatives of differentkinds.

Where tri-oxide of molybdenum is em ployed as an oxidant, Phave foundthatthis material becomes sticky or gummy as it changes from the higheroxide to one of the lower oxides while the reaction is taking place. Inmy early experiments, I employed furnaces of the rotating kiln typewhich are fitted with scrapers actlng on the oxide as it traveledthrough the reaction zone. In this operation trouble was experienced dueto the sticking and gumming of the oxide and in the several types ofapparatus herein shown, means are provided for overcoming thisdifficulty.

Referring to the embodiment of the invention illustrated in Figures 1and 2, 2 is a hopper or bin containing the powdered oxidant and 3 asupply pipe for thefluid hydrocarbon or other organic compound to betreated. Branch pipes 4 lead from the pipe 3 to stoves 5, eachcontaining a heating coil 6 for vaporizing the material to be oxidized.A valve 7 is provided for regulating the flow of hydrocarbon to eachstove: Suitable heaters 8 are provided in each stove, these being shownas gas heaters supplied from a gas line 9 and regulated by valves 10'.

Each heating coil 6 has a downwardly ex tending leg 11 terminatinginside a common treating chamber 12. This chamber is made of asubstantially gas-tight metal casing 13 provided with suitableinsulation 14 to conserve the heat. The legs 11 terminate in ahorizontal head- I er 15 provided with nozzles 16 by which the"vaporized or gaseous hydrocarbon from the v heater 6 is jetted acrossthe treating chamber 12. Outlets 17 are provided on the side of thetreating chamber 12 opposite the nozzles '16,. and a slot 18'f0rsupplying powdered oxidant from the hopper 2 extends along the top ofthe treating chamber. Suction means (not shown) are preferably providedfor causing the vapors leaving the nozzles 16 to travel across thechamber and find on outlet through the openings 17, and in their travelthe vapors encounter the screen S of powdered oxidant issuing fromv theslot 18. A bafile '19 is provided so that the path of the vapors leavingthe nozzle is substantially as indicated by the arrows. Thebaflle ispreferably used to reduce the carrying out of spent oxidant with thegasstrea'm. The solid oxidant tends to. drop'out of the stream as itvaried in len h to vary the time of contact of the gas an the oxidant inaccordance with 'the materials used, etc.- case of natural gas, forexample, the tempera- I before it enters-the chamber and the quantitysupplied should also be carefully regulated. I provide means between thehopper 2 and the slot 18 for attaining both these objects.

The hopper is provided at its bottom with a screen 20 over which therelies a slide 21. This slide consists of side members 22 and crossmembers 23 and the entire slide is adapted for reciprocation at anydesired speed. The reciprocating means is shown in the drawings asconsisting of a variable speed motor 24, suitable gearing 25, and acrank disk 26 connected to the slide by a connecting rod 27. By varyingthe speed of the motor 24 the slide 21 can be reciprocated at anydesired rate and the flow of powdered material thus controlled.Thescreen 20 is preferably carried in a withdrawable slide member 28 foreasy replacement.

The material passing through the screen 20 falls through a chamber 29 inwhich it is raised to the desired temperature. Theopenings 34 in thebaflies. This arrangement.

maintains the wall 31 at a high temperature and insures proper heatingof the oxidant. The other wall may be heat insulated as shown or may beheated in the same Way. The chamber 29 terminates in the slot 18 andwill be seen fromFigure 2 that a clear path s provided from the hopperinto the treating chamber 12. This is desirable as the material usedtends to become sticky at higher temperatures and caremust be used toprevent it from collecting or building up at any point.

- To prevent the material from clogging the slot 18 I provide in thechamber 29 a reciprocating plate 35 having aportion 36 extendingadjacent or into the slot 18. The plate 35 is mounted on a rod 37 whichextends outside the heating chamber 29 and is provided with an extension38 connecting the rod to the slide 21. Antifriction bearing balls 39 areprovided adjacent the portion 36 so that the entire plate mayreciprocate freely. This arrangement efl'ectually prevents clogging ofthe slot 18. Adjusting nuts 40' are provided so that the plate 35 may beraised or lowered as desired. It is therefore eflective not only forkeeping the slot 18 free of obstruction but also acts as a regulator forthe width of the slot whereby a supplemental adjustment opening in thechamber 29, these openings being provided with covers 41.

The spent oxidant falls to the bottom of the treating chamber 12 whereit collects in a pile' on a slide 42. At desired intervals the materialis withdrawn from the chamber by pushing a slide 43 inwardly so as toseal off the lower portion of the chamber and then withdrawing the slide42 so that the material thereon falls into a box 44, after which it maybe suitably treated and then returned to the hopper 2. The slide 43substantially prevents the ingress of air to the treating chamber 12 andpermits continuous operation of the apparatus without its being affectedby outside conditions. The powdered material collects on the slide 43while the material therebelow is being dumped and the side wall 12 ofthe chamber 12 in each case acts as a stripping means for breaking thematerial loose from the slides 42 or 43 in case'it should tend toadhere.

Referring now to the embodiment of the invention illustrated in Figures3 to 7, the oxidant instead of being used in powdered form is carried byprevious screens 50. In a complete cycle of the process the hothydrocarbon vapors or gases are passed through one of these pads and arethus oxidized, after which the pad is again supplied with oxygen,preferably by subjecting it to heated air. In order to carry out thesesteps I provide a heating chamber 51 divided into two compartments 52and 53 by a wheel 54 provided with a series of openings 50 in which thescreens 50 are secured. The periphery of the wheel fits into a recess 55which acts as a seal so that substantially the only comunication betweenthe portions 52 and 53 of the chamber is through the screens 50. Hot airis supplied to the chamber 52 through a conduit 56 at one side and belowand this air passes through the screens 50 and finds an outlet through astack 57 at the other side of the top. The hot air reoxidizes theoxidant screens for the next treatment of the hydrocarbon vapor, gas orother organic compound being treated.

The oxidation of the hydrocarbons is carried out at a treating stationindicated generally by the reference character T and the screens aresuccessively carried through this station by rotating the wheel 54. InFigure 3 there is shown a motor 58 connected to the shaft 59 of thewheel through suitable gearing 60 for causing rotation of the wheel atany desired speed.

The heated vapor is supplied from a conduit 61 having a downwardlyextending por tion 62 and a horizontal portion 63 extending into thetreating station. The construction is shown in detail in Figures 6 and7. The conduit 63 terminates in a contact member 64 which terminates ina cheek plate 65 and is slidably mounted in the frame 66.

The cheek plate 65 fits into an annular recess 67 in the wheel 51 and itwill be noted from Figures 5 and 6 that the openings 50 in which thepads 50 are fitted terminate in the recess. The contact member 64 isprovided with an opening 64 adapted to register with one of the openings50, while the cheek plates 65 extend vertically so as to cover theadjacent openings 50 and thus prevent any leakage of hydrocarbon vaporsfrom the conduit' 63 into the chamber 52 proper. The annulus 67 isprovided with packings 68 extending entirely around the wheel, whichserve to materially reduce leakage. Leakage is further prevented by theprovision of springs 69 carried by studs 70, mounted in the frame 66 andbearing against a collar 71 secured to the contact member 64. By thisarrangement the contact member is continually urged against the Wheeland a relatively tight sliding joint is secured.

The contact member 64 is du lieated on the other side of the wheel, thiseing indicated in Figures 6 and 7 at 64. The contact member 64 isprovided with a cheek plate 65 which is coextensive with the cheek plate65, as best shown in Figure 7.

In operation the vapors to be treated enter through the pipe 63, passthrough one of the screens 50 and leave the treating station through aconduit 72. The conduit 72 leads into a downwardly extending conduit 73conpected to an outlet 7 4 through a swivel joint It will be noted thatthe arrangement of inlet and outlet conduits is such that there is ageneral downflow of the vapors at all times, so that no condensedhydrocarbons can collect anywhere in the apparatus. As shown in Figure 7the openings through the contact members 64 and 64 are so arranged thatcondensed vapors cannot collect therein.

The frame 66 is slidably mounted in a guide 76 built into the furnacewall to permit movement of such frame toward or away from the center ofthe furnace with expansion or contraction of the wheel. In apparatus ofthis character the variation in wheel diameter will be a material amountand the arrangement shown prevents jamming of the apparatus. The frame66 is provided with interior flanges 77 which are packed to preventleakage. With the movement of the frame 66 inwardly or outwardly, it isof course necessary to move the conduits 63 and 72 correspondingly andthe swivel joint 75, together with a similar swivel joint (not shown)on' the conduit 61, make this movement possible. Packings 78 areprovided on the contact members 64 and 64' for the conduits 63 and 72 sothat expansion longitudinally of these conduits may be provided forwhile maintaining a tight joint and at the same time permit the slightrotation of the conduits which will be occasioned on a movement of theframe 66.

The wheel illustrated in Figures 3 to'l' has been shown as continuouslyrotated, but

a it will be understood that-a Geneva movement or similar apparatus forproviding an intermittenmotion on the wheel may be,-pro Vided ifdesired. As shown 'inFigure'7, the screens 50 are separated from oneanother only a relatively short distance and when so arranged thecontinuous rotation is. ad-vantageous. I 1

The treating chamber is maintained at suitable temperature by the hotair entering through the opening 56 and the treating station T is solocated with respect'to the-opem 5 shown as connected topins 92. at theupper pansion and contraction- This species of 1 Figures 3' to 7 is-notspecifically claimed herein, although it is covered and included withinthe broader method-and apparatus claims. It is covered'in. a divisionalappli cati zon, Serial No. 212,103filed August 10, 192

Referring to Figures 8' and 9, I show in these figures a system andapparatus which I have employed in the carrying out of the process. InFigure '9, 79 represents a stationarytubular'casing mounted in aninclined position and carried on upper and lower supports 80 and 81.Through the center of this tubular casing extends a rotary tube 82,rotated by pulley 83 and, to the upper end of which the stream of vaporor gas is supplied." The oxidant enters thewworm' feed chamber 84through channel 85, the worm'86 driven by pulley 87 carrying thematerial up into the upper portion of the tubular cas-' .ing. Externalheat is applied to the lower portion of the tubular casing, as forexam-'.

ple, by a burner conventionally shown at 88, to bring the reactiveelements to there active range. The upper; part of the stationarytubular casing is preferably pro vided Witha surrounding jacket ofnon-conducting material 89.. Thisheat is applied to the descendinggranular oxidant which, in turn; heats the gas or-vapor streampassingdown through the inner rota-ting tube. Theheated' stream of vapor orgaspreferably emerges from the inner tube at about .they

point marked A and contacts with the heated stream or shower of theoxidant, both passing out through the connection 90 into a closed trapor reservoir. A chain 91 is and lower portions. of the inner tube withinthe tubular casing and the inner rotation of- I 4 1 the inner tube. Thischain has a hammering and scraping effect giving a more uniform flow ofthe oxide down through the casing.

and particularlythrough the reaction zone,

stirrlng it up and causing it to feed-out in spite of its stickiness.

Thereceptacle into which the vapor and oxide material are fed is -keptsufiiciently' heated to allow the products of oxidation to remain invapor condition until they are car.-

.ried on into the absorbing system, preferably 7 0 comprising condensersand scrubbers.

In the preferred form, the general arrangement-is shown in the diagramof Figure'8',

wherein a cycling system is disclosed which" a it will-be understoodgenerally from the names applied tothe various parts. The partial 5oxidation chamber 79 proper is shown in Figure 8 in the center of thediagram, the oxidant material being fed in through channel I 85 from thereservoir 93 for fresh or revivifiedoxidant material. 94 is the'motorarj-- ranged to drive the pulley 83'fixed tothe H rotary tube 82 and. 95is another motor arranged to drive the circulating pump 96"an'dalso'through the reducing gear. 97,. the 'oxi-.

dant feed from the freshoxide' reservoir. 98

indicates a supply of raw gas feeding to the V, gas reservoir 99 fromwhich the gasis led" through valve pipe 100 tothe gas tube 82 of thepartial oxidation] chamber. 101 is the spent oxide receiver and 102 is.a-dust col-" lecting chamber. Both the spent oxide re 'ceiver and thedust collector are heated so that'the products of partial oxidation, canbe carried overinto the recovery system.

These products pass from the dust collector 102 through water condenser103 to overflow trap .104 and thence through scrubbers and overflowtraps as shown.- The residual gas stream passes from the last scrubberto the receiver 105 and thence through pipe 106 having bypass'107withthe gas sampling tube and back to the pump 96. F-romthe pump .96 itpasses tothe-treated gas reservoir 108, I this having-ja pressureregulator and a tapout as .shown,and from this treated gas reservoir itpasses through tube 109 back tothe. inlet-to the partial oxidationchamber where I it meets the fresh stream coming fromthe, f

raw reservoir 99. v

' In carrying out my process with the above described apparatus, thetemperatures were recorded'by athermocouple placed either 'at the centerofthe outlet from the stationary I casing or on the outer wall ofsaidoutlet.

The readings from the outer wall were'about 100 C. higher'than thosefrom the thermo-v couple when let passage.

Inasmuch as natural placedat the center of the'outgas requires a higherreaction temperature than heavier gases, I experimented with hydrocarbongases heavier.-

than methane. For example, the so-called liquid gas made from casinghead as by removal of the gasoline therein. This was supplied in liquidform and consisted of ethane about 20%, propane about 60% and butaneabout 20%. In the first run with this material, the rate of gas flow wasliter per minute (Without cycling) and the feed of molybdenum tri-oxidewas approximately 4.3 grams per minute. The temperature at the spentoxide exit was 400 C. The length of the run was 2 hours. A sample of thegas collected at about the middle of the run when conditions weresubstantially normal showed the following by volume: P

er cent Carbon dioxide (CO None Oxygen (O2) Unsaturated hydrocarbons ofthe CnH n series Carbon monoxide Non The products caught in the waterscrubbers on one passage were:

Per cent Aldehyde (calculated as propionic) based on Weight of gas fed.096 Acid (calculated as propionic) based on weight of gas calculated aspropane .42

This run showed that a higher temperature was needed, so the next runwas as follows: rate of gas flowliter per minute (without cycling) Rateof oxide (M00 feed--5.65 grams per minute Temperature-400 C. Length ofruntwo hours The gas analysis with percentages by volume gave:

Perc nt Carbon dioxide 00. 5.4 Oxygen (O2) .2

Unsaturated hydrocarbons of the CnH n series Carbon monoxide None Lengthof run45 minutes The gas analysis showed:

Per cent Carbon dioxide 5.8 Oxygen 1.3 Unsaturated hydrocarbons 2.9Carbon monoxide None The products showed: P

er cent Aldehyde (calculated as propionic) 1.77 Acid (calculated aspropiomc) 2.55

The gas analysis showed:

Per cent Carbon dioxide 13.0 Oxygen None Unsaturated hydrocarbons 2. 8Carbon monoxide None The products from the absorbing system showed:

Percent Aldehyde (calculated as propionic) 3. 95 Acid (calculated asproplonic) 4.07

These are based on the weight of gas calculated as propane.

Since the remainder of the exit gas is unchanged hydrocarbon,calculating the above acids and aldehydes as a percentage of the gasactually attacked, the results showed that approximately 53% of the gasso attacked passed into-acid and aldehyde in the proportion above given.

Rwnzi Rate of gas flow liter per minute (without cycling) Rate of oxidefeed-42 grams per minute Temperaturemeasured on the outside of the exittube-500 C., giving an estimated temperature of 600 C. at the inside ofthe exit.

The gas analysis was:

These are based on the weight of gas calculated as propane. Thispercentage of product is 41.5% of the hydrocarbon actually attacked, theremainder being unchanged in the exit gas.

The aldehyde and acid in the above tests were calculated to the propanederivatives, since the gas treated was 60% propane at the beginning andas the liquid evaporated, this would give a gas largely propane at aboutthe middle of the tank contents. The evidence also shows that the-acidwas largely propionic.

In the above experiments, the gas was not cycled. From the calculationswhere the acid and aldehyde are based on the hydrocarbon actuallyattacked, it will be seen that the products represent from 40% to 50% ofthe hydrocarbon actually attacked. Hence, the unchanged hydrocarbonshould be converted by resubjecting it to the process either in the sameor successive apparatus. It will further be noted that the carbondioxide in the exit gas will (by the mass action efiect) serve to reduceand retard the formation of more carbon dioxide on the second andfurther passages. Hence, by cycling the gas, the yields will amount toat least 50%"of the total hydrocarbon treated.

In carrying out the cycling operation, I may employ the apparatus ofFigure 8, in

which case the gas is supplied to the inner.

rotary tube of the oxidationchamber while at the same time fresh oxideis fed around the tube into the upper end of said chamber. After itsdescent through this stationary tube the oxidant becomes heated andthereby heats the gas in the tube. The gas then issues from the tubetoward its lower portion and meeting the oxidant withdraws oxygentherefrom.

The gas mixture and the spent oxidant, then pass out into the spentoxide receiver 101,- thence through the dust collector, water condenser,scrubbing system, etc., back to the circulating pump which feeds theresidual gas stream into the treated gas reservoir where a portion maybe tapped out as above described if desired. From the treated gasreservoir the gas is then passed through suitable controls back to theentrance to the partial oxidation chamber where it is mixed with thefresh gas coming from the raw gas reservoir.

I have also found that the sticking or gumming of the molybdenum oxidein the reactive zone may be reduced or partly obviated by adding finelydivided inert material to the powdered oxidant. Thus, I may employ withthe oxidant an equal volume of uni-- formly'graded fine silica sand withadvantage. In this case, the passage through the apparatus was moreeasily accomplished.

It will be noted that in all cases, the hydrocarbon in vapor or gaseousphase or other finely divided condition is brought in contact with anoxidant under a temperature such as to give a reaction, causing oxygento leave the oxidant and become chemically tied into the hydrocarbon.The temperature will vary from a relatively low temperature where thevapor or gas stream contains a large amount ofrunsaturated compounds,such as cracln'ng still gases, to a relatively high temperature around500 to-600 or 700 C. inthe case of methane or fixed gases requiringhigher temperatures for the reaction.

urated aliphatic hydrocarbons. The method may be used for the productionof valuable products from unsaturated hydrocarbons of the aliphaticseries, as well as from naphthenic, terpenic and aromatic hydrocarbons.

Thus, the process is readily adapted to the roduction of benzaldehydeand benzoic acid rom toluene, as well as to the production of phthalicanhydride from naphthalene and V to the production of maleic acid frombenzene.

It may also be applied to the treatment of alcohols to form aldehydesand acids, such.

for example, as ethyl alcohol or other derivatives as the raw materialtreated, or to mix,

, tures of hydrocarbons and hydrocarbon derivatives. v

I consider myself the first to partially oxi- I prefer to employ a shorttime of sojourn dize hydrocarbons in the vapor or gaseous phase by meansof oxygen derived from a material in which the oxygen is chemicall combined and is transferred from the oxi ant to the hydrocarbon orhydrocarbon derivative in the reaction zone. While the class of oxidantsI have disclosed is preferable, other oxidants may be employed.

In carrying out my process I may employ 1 either sub-atmosphericpressure or super-' atmospheric pressure within the partial oxi- ,dationchamber. In the form where the rotary carriage having catalytic screensis employed in the vapor feed pipe and the outlet pipe may be moved in acircular path instead of moving the screens. In other words the movementmay be relative.

The advantages of my invention are especially important in connectionwith lighter hydrocarbons, although the process may be employed onheavier hydrocarbons.

By the term solid oxidant material in my'claims,"I intend to cover anysolid material which, under the general conditions recited herein,willyield oxygen to the organic material and become chemically tiedthereinto, and which oxidant material if reused in the process,,must berenewed or revivified by adding oxygen thereto, this being preferably ata point removed from the reaction zone and at a higher temperature thannormally exists in the reaction zone, such temperature being obtained bythe addition of heat.

I do not claim herein the metallurgical method of reducing metallicoxides to metals herein disclosed, as that invention is covered in theclaims of my copending divisional application Ser. No. 550,147, filedJuly 11,1931.

I claim:

1. In the method of partially oxidizing organic bodies, the stepsconsisting of feeding in finely divided condition an organic bodycontaining hydrogen and carbon as its major constituents in asubstantially non-oxidizing atmosphere into contact with solid oxidantmaterial at a reactive temperature, said oxidant material being capableof yielding oxygen to the organic body, thereby causing oxygen to passfrom the oxidant material into the organic body, and withdrawing theoxidant material from the reaction zone and reoxidizing it.

2. In the method of partially oxidizing organic bodies, the stepsconsisting of feeding in finely divided condition an organic bodycontaining hydrogen and carbon as its major constituents in asubstantially non-oxi' dizing atmosphere into contact with solid oxidantmaterial at a reactive temperature, said oxidant material being capableof yielding oxygen to the organic body, thereby causing oxygen to passfrom the oxidant material into the organic body, and withdrawing the0x1- dant material from the reaction zone during a reaction period.

3. In the method of partially oxidizin organic bodies, the stepsconsisting of fee ing in finely divided condition an organic bodycontaining hydrogen and carbon as its major constituents in asubstantially non-oxidizing atmosphere into contact with solid oxidantmaterial at a reactive temperature, said oxidant material being capableof yielding oxygen to the organic body, thereby causing oxygen to passfrom the oxidant material into the organic body, and withdrawing the0x1- dant material from the reaction zone during a reaction period andreoxidizing it.

4. In the method of partially oxidizing organic bodies, the stepsconsisting of feeding in finely divided condition an organic bodycontaining hydrogen and carbon as its major constituents in asubstantially non-oxidizing atmosphere into contact with solid oxidantmaterial at a reactive temperature, said oxidant material being capableof yielding oxygen to the organic body, thereby causing oxy gen to passfrom the oxidant material into the organic body, and withdrawing theoxidant material from the reaction zone and reoxidizing it and reusingit in such process.

5. In the method of partially oxidizing organic bodies, the stepsconsisting of feeding in finely divided condition an organic bodycontaining hydrogen and carbon as its major constituents in asubstantially non-oxidizing atmosphere into contact with solid oxidantmaterial at a reactive temperature, said oxidant material being capableof yielding oxygen to the organic body, thereby causing oxygen to passfrom the oxidant material into the organic body, and withdrawing theoxidant material from the reaction zone and reoxidizing it.

6. In the method of partially oxidizing organic bodies, the stepsconsisting of passing through a hot reaction zone having a substantiallynon-oxidizing atmosphere, solid oxidant material which will yield oxygento an organic body, passing an organic body containing carbon andhydrogen as the major constituents in finely divided condition throughsaid reaction zone in contact with the oxidant material at a reactivetemerature, thereby causing oxygen to pass rom the material into theorganic body, and withdrawing the oxidant material.

7. In the method of partially oxidizing organic bodies, the stepsconsisting of passing through a hot reaction zone having a substantiallynon-oxidizing atmosphere, solid oxidant material which will yield oxygento an organic body, passing an organic body containing carbon andhydrogen as the major constituents in finely divided condition throughsaid reaction zone in contact with the oxidant material at a reactivetemperature, thereby causing oxygen to pass from the material into theorganic body, and withdrawing the oxidant material and reoxidizing it.

8. In the method of partially oxidizing organic bodies, the stepsconsisting of passing through a hot reaction'zone having a substantiallynon-oxidizing atmosphere, solid oxidant material which will yield oxygento an organic body, passing an organic body containing carbon andhydrogen as the major constituents in finely divided condition throughsaid reaction zone in contact with the oxidant material at a reactivetemperature, thereby causing oxygen to pass from the material into theorganic body, and withdrawing the oxidant material during a reactiveperiod.

9. In the method of partially oxidizing organic bodies, the stepsconsisting of passing through a hot reaction zone having a substantiallynon-oxidizing atmosphere, solid oxidant material which will yield oxygento an organic body, passing an organic body containing carbon andhydrogen as the major constituents in finely divided condition throughsaid reaction zone in contact with the oxidant material at a reactivetemperature, thereby causing oxygen to pass from the material into theorganic body, and withdrawing the oxidant material and reoxidizing itand reusing it in such process.

10. In the method of partially oxidizing organic bodies, the stepsconsisting of passing through a hot reaction zone having a substantially non-oxidizing atmosphere a relatively thin layer of solidoxidant material which will yield oxygen to an organic body,

passing an organic body containing carbon and hydrogen as the majorconstituents in finely divided condition through said reaction zone incontact with the oxidant material at a reactive temperature, therebycausing oxygen to pass from the material into the organic body, andwithdrawing the oxidant material.

11. In the method of partially oxidizing organic bodies, the stepsconsisting of pass ing through a hot reaction zone having asubstantially non-oxidizing atmosphere, solid oxidant material whichwill yield oxygen to' an organicibody, passing an organic bodycontainingcarbon and hydrogen asthe major constituents in finely dividedcondition through said reaction zone in contact with the oxidantmaterial at a reactive temperature, thereby causing oxygen to pass fromthe material into the organic body, and trapping out the oxidantmateriaL' 12. In the method of partially oxidizing organic bodies, thesteps consisting of passing through a hot reaction zone having a tillsubstantially non-oxidizing atmosphere finely divided solid oxidantmaterial which will yield oxygen to an organic body, passing an organicbody containing carbon and hydrogen as the major constituents in finelydivided condition through said reaction zone in contact with the oxidantmaterial at a reactive temperature, thereby causing oxygen to pass fromthe material into the organic body, and withdrawing the oxidantmaterial.

13. In the method of partially oxidizing organic bodies, the stepsconsisting of passing an organic body containing carbon and hydrogen asthe major constituents while in finely divided condition in contact withsolid oxidant material which will yield oxygen to the organic body andwill reoxidize on exposure to oxygen, in a substantially non-oxidizingatmosphere at a reactive temperature, thereby causing oxygen to passfromthe oxidant material into the organic body, and cycling at least a partof the exit stream through such a reaction zone.

14. In the method of partially oxidizing organic bodies, the stepsconsisting of pass ing an organic body containing carbon and hydrogen asthe major constituents while in finely divided condition in contact withsolid oxidant material which will yield oxygen to the organic body andwill reoxidize on exposure to oxygen, in a substantially non-oxidizingatmosphere at a reactive temperature, thereby causing oxygen to pass.from the oxidant material into the organic body, and cycling at least apart of the exit stream including carbon dioxide.

15. In the method of partially oxidizing organic bodies, the stepsconsisting of vpassing an organic body containing carbon and hydrogen asthe major constituents while in finely divided condition in contact withsolid oxidant material which will yield oxygen to ing an organic bodycontaining carbon'and hydrogen as the major constituents while in finelydivided condition in contact with solid oxidant material Which willyield oxygen to the organic body and will reoxidize on exposure tooxygen, in a substantially'non-oxidizin atmosphere at a reactivetemperature, therel iy causing oxygen to pass from the oxidant materialInto the organic body, removing products from the exit stream, adding anorganic body of the same type and again passin the mixture through areactive zone.

17. In the method of making organic compounds, the steps consisting offeeding. a stream of an organic compound of the hydrocarbon type throughan enclosed reactive zone, bringing it into contact in said zone withsuccessive portions of a solid chemical compound, chemically tying anelement of the solid chemical compound into said organic compound, andWithdrawing and recovering products from the stream.

18. In the method of making organic compounds, the steps consisting offeeding a stream of an organic compound of the hydrocarbon type throughan enclosed reactive zone, bringing it into contact in said zone withsuccessive portions of a solid chemical compound at a temperature belowred heat, chemically tying a normally gaseous element of the solidchemical compound into said organic compound, and withdrawing andrecovering products from the stream.

19. In the method of making organic compounds, the steps consisting offeeding a stream of an organic compound through an enclosed reactivezone, passing all'parts of said stream through and in intimate contactin said zone with successive portions of asolidchemical compound,chemically tying a normally gaseous element of the solid chemicalcompoundinto said organic compound, and withdrawing and recoveringproducts from the stream.

20. In the method of making organic compounds, the steps consisting offeeding a stream of an organic compound of the hydrocarbon type throughan enclosed reactive zone, bringing it into contact in said zone withsuccessive portions of a solid chemical compound at a temperature belowatemperature of continuous self-sustained combustion, chemically tying anormally gaseous element of the solid chemical compound into saidorganic compound, and withdrawing and recovering products from thestream.

21. In the method of partially oxidizin organic bodies, the stepsconsisting of fee ing a gaseoushase stream of a compound containing hyrogen and carbon through a hot reaction zone havin a sufficient supply.of a non-gaseous chemica compound containing chemically'combined oxygenand having the property of releasing the combined oxygen under theconditions .in the hot reaction zone to supply oxygen to combine with amaterial proportion of the hydrogen-carbon compound, maintaining in saidzone reactive conditions which cause oxygen to be withdrawn from itscompound and combine with the hydrogen-carbon compound to form the majorportion of hydrogen-carbon-oxygen compounds produced therein and causlngrelative movement between the compounds to bring the gaseous-phasestream in contact with further non-gaseous oxygen-containing compounds.

22. In the method of partially oxidizing organic bodies, the stepsconsisting of feed- 1 ing a gaseoushase stream of a compound containinghy rogen and carbon through a hot reaction zone having a sufiicientsupply 'of a non-gaseous chemical compound containing chemicallycombined oxygen and having the property of releasing the combined oxygenunder the cond tions in the hot reaction zone to supply oxy en tocombine with a material proportion o the hydrogen- .carbon compound,maintaining in said zone reactive conditionswhichcause oxygen to be.withdrawn from its compound and combine withthe hydrogen-carboncompound to form the major portion of the hydrogen-carbonoxygencompounds produced therein, causing relative movement betweenthe'compounds to bring the gaseous-phase stream in contact with furthernon-gaseous oxy en-containing compounds, and regenerating thenon-gaseous ox gen-containing material by chemically com ining oxygentherewith.

23. In the method of partially oxidizing organic bodies, the stepsconsisting of feeding a gaseous-phase stream of a compound containinghydrogen and carbon'through a hot reaction zone havin'g-a sufiicientsupply of a non-gaseous chemical compound containing chemically combinedoxy en and having the property of releasingte combined oxygen under theconditions in the hot reaction zone to supply oxy en "tocombine with amaterial proportion'o the hydrogencarbon compound, maintaining insaidzone reactive conditions which causeoxygen to be withdrawn from itscompound and combine with the hydrogen-carboncompound to form the majorportion of hydrogen-carbon-oxygen compounds produced therein, causingrelative movement between the compounds to bring the gaseous-phasestream in contact with further non-gaseous oxygen-containing compounds,and supplying heat and oxygen to the non-gaseous oxygen-containingmaterial exteriorly of the reaction zone to regenerate it. I

24. In the method of partially oxidizing organic bodies, the stepsconsisting of feeding a gaseoushase stream of a compound containing hyrogen and carbon through a hot reaction zone havin a sufficient supplyof a non-gaseous chemical compound containing chemically combined oxy enand having the property of releasing t e combined oxygen under theconditions in the hot reaction zone to supply oxygen tocombine with amaterial proportion of the hydrogencarbon compound, maintaining in saidzone reactive conditions which cause oxygen to be withdrawn from itscompound and combine with the hydrogen-carbon compound to form the majorportion of hydrogen-carbonoxygen compounds produced therein, andsupplying fresh oxygen-containing material to t e reaction zone andremoving spent material therefrom.

25. In the method of partially oxidizing organic bodies, the stepsconsisting of feeding in a finely divided stream a compound containinghydro en and carbon said stream being substantial y free from treeoxygen, through a hot reaction zone having a sufficient supply of achemical compound containing oxygen and having the property of releasingt e oxygen under the conditions in the hot reaction zone to supplyoxygen to combine with a material-proportion of the hydrogen-carboncompound, maintaining in said zone reactive conditions which causeoxygen to be withdrawn from its compound and combine with thehydrogen-carbon compound to form the major portion ofhydrogen-carbon-oxygen compounds produced therein, and causing relativemovement between the compounds to bring the gaseousphase stream incontact with further oxygencontaining compounds.

26. In the method of partially oxidizing organic bodies, the ste sconsisting of feeding in a finely divide stream a compound containinghydrogen and carbon, said stream being substantially free from freeoxygen, through a hot reaction zone having a sufficient supply of achemical compound containing oxygen and having the property of releasingt e oxygen under the conditions in the hot reaction zone to supplyoxygen to combine with a material proportion of the hydrogen-carboncompound, maintaining in said zone reactive conditions which causeoxygen to be withdrawn from its compound and combine with thehydrogen-carbon compound to form the major portion ofhydrogen-carbon-oxygen compounds produced therein, causing relativemovement between the compounds to bring the gaseous-phase organicbodies, the steps consistingof feed-'.

ing in a finely divided stream a compound containing hydrogen andcarbon,said stream being substantially free from free oxygen, through ahot' reaction zone having a sum cient supply of a chemical compound containing ox gen and having'the property of releasing t e oxygen under theconditions in the hot reaction zone to supply oxygen to combine with amaterial proportion of the hydrogen-carbon compound, maintaining in.

said zone reactive conditions which cause oxygen to be withdrawn fromits compound and combine with the hydrogen-carbon com-- pound to formthe major portion of h drogen-carbon-oxygen compounds pro uced' therein,and supplying fresh oxygen-contain- 7 ing material to the reaction zoneand removing spent material therefrom. v

In testimony whereof I have hereunto set m hand.

y JOSEPH H. JAMES.

